Reaction product of aldehydes and triazine derivatives



plastics and coating arts. vention is concerned with compositions of matter Patented Apr. 27, 1943 REACTION rnonuo rnmznvn '1 OF ALDEHYDES AND DERIVATIVES Gaetano F. DAlelio and James W. Underwood,

Pittsfleld, Mass.,-assignors to General Electric Company, a corporation of-New York No Drawing. Application June 27, 1941,

Serial No. 400,148

19 Claims.

- This invention relates to the production of new synthetic materials and more particularly to new reaction products of particular utility in the Specifically the incomprising a condensation product of ingredients comprising an aldehyde, including polymeric aldehydes and aldehyde-addition products, e. g.,

' formaldehyde, paraformaldehyde. dimethylol urea, trimethylol malamine, etc., and an striazinyl ,carbamyl-alkyl sulfide (s-triazinylthio-acy'lamide) or an s-triazinyl thiocarbamylalkyl sulfid (s triazinyl thiacylthioamide) corresponding to the following general formula:

3nl- N N J c I In the above formula 11. represents an integer and is at least 1 and not more than 3, a; is an integer and is at least 1 and not more than 2, Y represents a member of the class consisting of oxygen and sulfur, and R represents a member of the class consisting of hydrogen and monovalent hydrocarbon and halo-hydrocarbon radicals, numerous examples of which hereafter are given. Since :0 represents an integer which is 1 or 2, it will be seen that the linkage of the carbamyl-alkyl (or thiooarbamyl-alkyl) group to the sulfur atom in all cases will be alpha or beta to the carbamyl (CONHR) or thiocarbamyl (-CSNHR) group. It also will be observed that linkage of the triazinyl grouping to th sulfur atom is through a carbon atom. From a consideration of the formula it further will be seen that when n is 3 there will be no amino (NHR) groups attached to the triazine nucleus. Instead of the s-triazinyl carbamyl-alkyl and thiocarbamyl-alkyl sulfides represented by the above chlorcyclohexyl,

ethyl chlorphenyl, phenyl chlorethyl', bromethyl,

chlormethyl, dichlorphenyl,

bromtolyl, etc. Preferably R is hydrogen.

More specific examples of s-triazinyl carbamylalkyl and thiocarbamyl-alkyl'sulfides that may be employed in producing our new condensation products are s-triazinyl tri-(carbamyi-methyl sulfide), s-triazinyl tri-(carbamyl-ethyl sulfide),

formula, corresponding derivatives of the asymmetric triazines or of the vicinal triazines may be used.

Illustrative examples of monovalent hydrocarbon radicals that R. in the above formula may represent are aliphatic (e. g., methyl, ethyl, propyl, isopropyl, butyl, secondary butyl, isobutyl, amyl, isoamyl, hexyl, etc.), including cycloaliphatic (e. g., cyclopentyl, cyclopentenyl, cyclohexyl, cyclohexenyl, cycloheptyl, etc.) aryl (e. g., phenyl, diphenyl, naphthyl, etc.); alkaryl (e. g., tolyl, xylyl, ethylphenyl, propylphenyl, isopropylphenyl, etc.); aralkyl (e. g., benzyl, phenylethyl, phenylpropyl, etc.) and their homologues, as well as-those groups with one or'more of their hydrogen atoms substituted by, for example, a halogen. Specific examples of halogeno-substituted hydrocarbon radicals are chlorphenyl,

diamino s-triazinyl tri-(thiocarbamyl-methyl sulfide), striazinyl tri-(thiocarbamyl-ethyl sulfide), the monoamino ('NHR) s-triazinyl di-(carbamylmethyl sulfides), the monoamino (-Nlflt) striazinyl di-(thiocarbamyl-methyl sulfides), the monoamino (-NI-IR) s-triazinyl di-(carbamylethyl sulfides), the monoamino (-NI-IR) striazinyl di-(thiocarbamyl-ethyl sulfides) the [(NI*IR)-il s-triazinyl mono-(carbamyl-methyl sulfides), the diamino [(-NHR) a] s-triazinyl mono- (thiocarbamyl-methyl sulfides) the diamino [(-NHR)2] s-triazinyl mono- (carbamyl-ethyl sulfides), and the diamino [(-NHR)2] s triazinyl mono (thiocarbamylethyl sulfides).

The triazinyl carbamyl-alkyl and thiocar- I bamyl-alkyl sulfides that are used in carrying the present invention into eifect are mor fully described and are specifically claimed in our copending application Serial No. 400,151, filed concurrently herewith, now Patent No. 2,295,562, issued September 15, 1942, and assigned to the same assignee as the present invention.

Other and more specific examples of triazinyl carbamyl-alkyl and thiocarbamyl-alkyl sulfides that may be used in producing our new condensation products are listed below:

4,6-diamino s-triazinyl-2 thiocarbamyl-methyl sulfide s Triazinyl' 2,4,6 tri-(beta-carbamyl-ethyl sulfide) Y 6 amino s triazinyl 2,4- di- (carbamyl-methyl sulfide) G-amino s-triazinyl-ZA di-(thiocarbamyl-methyl 4,6 diamino s triazinyl-2 beta-cyclohexylthio-.

carbamyl-ethyl sulfide products of an aldehyde initiated under alkaline conditions.

4,6 diamino s triazinyl-2 alpha-thiocarbam'ylethyl sulfide 4,6-di-(methylamino) s-triazinyl-2 beta-(alphacyclohexyl carbamyl-butyl) sulfide 4.6-di-toluido s-'triazinyl-2 beta-(gamma-phenyl methyl-thiocarbamyl-propyl) sulfide 4,6 di (cyclohexylamino) s -triazinyl-2 alphaphenylthiocarbamyl-propyl sulfide 6 naphthylamino s triazinyl 2,4 di (alpha-' phenylcarbamyl-propyl sulfide) 6-ethylamino s-triazinyl- 2,4 di-(carbamyl-chlorphenyl-methyl sulfide) I s-Triazinyl-2,4,6 tri-(benzylthiocarbamyl-methyl sulfide) k s-Triazinyl-2,4,6 tri-[beta-(alpha-phenyl carbamyl-butyl) sulfide] 6 amino s triazinyl Z-thiOcarbamyI-methyl 4- carbamyl-methyl disulfide I v The formulas for the above compounds are shown in our above-identified copending applica- -tion Serial No. 400,151,

The present invention is based on our discovery reactable, e. g., tertiary amines such as triallqrl (e. g., trimethyl, triethyl, etc.) amines, triaryl (e. g., triphenyl, tricresyl, etc.) amines, etc., and

(,2) nitrogen-containing basic compounds that are aldehyde-reactable, for instance ammonia, primary amines (e. g., ethyl amine, propyl amine, etc.) and secondary amines (e. g., dipropyl amine, dibutyl amine, 'etc.). The secondary condensation catalyst, which ordinarily, is used in an amount less than the amount of the primary catalyst, should be a fixed alkali, for instance, a

carbonate, cyanide or hydroxide of an alkali metal (e. g., sodium, potassium, lithium, etc). I Illustrative examples" of acid condensation catalysts that may be employed are inorganic or organic acids such as hydrochloric, sulfuric, phosphoric, acetic, lactic, acrylic, malonic, etc.,

or acid salts such as sodium acid sulfate, monosodium phosphate, monosodium phthalate, etc.

that new and valuable materials of particular utility in the plastics and coating arts can be produced, by effecting reaction between ingredients comprising essentially an aldehyde, including polymeric aldehydes and aldehyde-addition products, and certain triazinyl carbamylalkyl or triazinyl thiocarbamyl-alkyl sulfides, numerous examples of which have been given above and in our above-identified copending application.

Resins heretofore have been made by condensing an aldehyde with certain thioammeline ethers, but such known resinsare' not entirely satisfactory fromrthe standpoint of optimum heat-, waterand abrasion-resistance and in curing characteristics. One possible explana-- tion for these deficiencies in desirable properties is the fact that the starting material contains thio groups that are aldehyde-non-reactable. In marked contrast the starting organic sulfides used in practicingthis invention con.-

tain aldehyde-reactable thio groups attached to the triazine nucleus, thereby imparting to the condensation products of such sulfides with aldehydes increased heat-,water-' and abrasionresistance and improved curing characteristics as compared with known resinous condensation and a thioammeline ether.

In practicing our invention the initial condensation reaction may be carried out at normal or at elevated temperatures, at atmospheric. subatmospheric orsuper-atmospheric pressures and under neutral, alkaline or acid conditions. Preferably the reaction between the components'is Any substance yielding an alkaline or an acid aqueous solution may be used in obtaining alka-.

line or acid conditions for the initial condensation reaction. For example, we may use an alka-.

line substance such as sodium, potassium or calcium hydroxides, sodium orpotassium carbonates, mono-, dior'tri-amines, etc. Good results are obtained by causing the condensation reaction between the primary components to Mixtures of acids, of acid salts or of acids and of acid salts may be employed if desired.

The reaction between the aldehyde, e. g., formaldehyde, and the triazine derivative used by the applicants may be carried out in the presence or solvents or diluents, fillers, other natural or synthetic resinous bodies, or whileadmixed with other materials which also can react with the aldehydic reactant or with the triazine deriva tive, e. g., ketones, urea, thiourea, selenourea, iminourea, (guanidine), substituted ureas, thioureas, selenoureas and iminoureas, numerous examples of which are given in various copending applications of one of us (Gaetano F. DAle1io),.

for instance, in DAlel'io copending application Serial No. 363,037, filed October 26, 1940; monoamides of monocarboxylic and polycarboxylic acids and polyamides of polycarboxylic acids,

cations, for instance, in DAlelio copending a'ppli cation Serial No. 377,524, filed Feb. 5, 194-1, and in applications referred to in' said copending application; aminodiazines and aminodiazoles; phenol and substituted phenols, e. g., the cresols, the xylenols, the tertiary alkyl phenols and other phenols such as mentioned in DAlelio Patentv 2,239,441; monohydric and polyhydric alcohols, e. g., butyl alcohol, amyl alcohol, ethylene glycol,

,glycerine, polyvinyl alcohol, etc. amines, including aromatic amines, e. g., aniline, etc.; and the like. 1 These modifying reactants may be incorporated with the triazine derivative and the aldehyde by mixing all the reactants and efiecting condensation therebetween or by various permutations of the reactants as described, for example,

in DAlelio copending applicatlon Serial No.

take place in the presence of a primary condensation catalyst and a secondary condensation catalyst. Condensation products of excellent timeor storage-stability characteristics are obtained by using as the primary catalysta member of the class consisting of (1) nitrogenecontaining basic tertiary compounds that are aldehyde-non 363,037 with particular reference to reactions involving a urea, an aldehyde and asemi-amide of oxalic acid; For instance, we may form a partial condensation product of ingredients comprising urea, a diafmino triazinyl carbamylmethyl sulfide and formaldehyde and thereafter efi'ect reaction between this partial condensation product. and, for example,' a chlorinated. acetamide to obtain'a heat-curable composition.

. Some of the condensation products of this invention are thermoplastic materials even at an advanced stage of condensation while others are thermosetting or potentially thermosetting bodies which convert under heat or under heat and pressure .to an insoluble, infusible state. Those materials which are slightly thermoelastic are particularly useful. in producing molding compounds suitable for use in 'making pieces to be molded over screws (as in making bottle caps). The thermoplastic condensation products are of particular utility as plasticizers for other synthetic resins. The thermosettingor potentially thermosetting condensation products, alone or mixed with fillers, pigments, dyes, lubricants, plasticizers, etc., may be used, for example, in the production of molding compositions.

The heat-curable resinous condensation products of this invention show good flow" characteristics during a short curing cycle. "This is a property that is particularly desirable in a molding "compound. The molded resins are of exceptionally light color. colors can be obtained by incorporating a suitable pigment into the molding compound. The molded articles have good surface finish and excellent resistance to water and arcing. They have a high dielectricstrength. The pH at which the heat-curable resins of this invention cure generally is of the order of 5.0 to 8.0. Basic fillers such as asbestos, therefore, can be used satisfactorily in the production of molding compounds without detrimental efiect upon the rapidity of cure of the compound.

Depending upon the particular reactants em:

ployed andthe particular conditions of reaction,

the intermediate or partial condensation products vary from clear, colorless or colored, syrupy, water-soluble liquids to viscous, milky dispersions and gel-like masses of decreased solubility in ordinary solvents, such as alcohol, glycol, glycerine, water, etc. These liquid intermediate condensation products may be concentrated or diluted further by the removal or addition of volatile solvents to form liquid coating compositions of adjusted viscosity and concentrations. The heat-convertible or potentially heat-convertible resinous condensation products may be used in liquid state, for instance, as surface-coating materials, in the production of paints, varnishes, lacquers, enamels, etc., for general adhesive applications, in producing laminated articles and for numerous other purposes. The liquid. heat-hardenable or potentially heat-hardenable condensation products also may be used directly as casting resins, while those which are of gellike nature in partially condensed state may be dried and granulated to form clear, unfilled heatconvertible resins.

In order that those skilled in the art better Products of any desired mass for 15 minutes, yieldinga clear resinous syrup having a pH of 7.61. Upon testing this -syrup on a 130 C. hot plate it was found to body slowly to a solid resin having a very high fusion point. The addition of a small amount (0.5 part) of chloracetamide (monochloracetamide) to the above resinous syrup, followed by refluxing for an additional 5 minutes to cause the chloracetamide to intercondense with the partial condensation product of the triazine derivative and formaldehyde, produced a resin that cured fairly rapidly to an insoluble, infusible state. A molding compound was produced by mixing this resinous syrup with parts alpha cellulose in flock form and 0.2 part of a mold lubricant, specifically zinc stearate. The wet molding compound was oven dried at C. for minutes, followed by drying at room temperature for a proximately 15 hours. A sample of the dried compound was molded for 3 minutes at C. under a pressure of 2,000 pounds per quare inch. The molded article was well-cured throughout and showed good flow characteristics during molding. The molded piece 'was very'resistant to water as evidenced by the fact that, when immersed in boiling water for 15 minutes followed by immersion in .cold water for 5 minutes, it absorbed only 2.7% by weight of I hydrochloride, nitrourea, glycine, sulfamic acid,

may understand how this invention may be carried into efiect, the following examples are given by way of illustration. All parts are by weight.

Aqueous ammonia (approx. 28% NH3) 4.0 Sodiumhydroxide in 2.5 parts water 0.05 Water 10.0

The above components were heated together under reflux at the boiling temperature of the amples are given in various DAlelio copending applications, for instance, in copending application Serial No. 346,962, filed July 23, 1940, and Serial No. 354,395, filed August 2'7, 1940, both of which applications are assigned to the same assignee as the present invention.

Were heated together under reflux for 30 minutes,

yielding a clear resinous syrup. This syrup cured slowly on'a 130 C. hot plate. The addition of 0.5 part chloracetamide to the syrup, followed by refluxing for an additional 10 minutes, produced a resin which cured to the insoluble, infusible state.

.A'molding compound was produced from the syrup. into which .the chloracetamide had been Water r I were heated together under reflux for minutes.

' characteristics during molding.

Waterintercondensed by mixing therewith 35 parts alpha flock and 0.2 part zinc'stearate. The wet compound was dried for 95 minutes at 56 C. A sample of the dried compound was molded for 4 minutes at 130 C. under a pressure of 2,000 pounds persquare inch. Themolded piece was light in color and had. a glossy surface flnish.

When the molded article was tested-for water absorption described under Example 1, it showed only 2.05% 'Water absorbed. -The flow of the molding compound during molding'was very ood. Similar results are obtained with molding periods of the order of 3 minutes.

Example 3 q v I I Parts 4,6-diamino s-triazinyi-2 carbamyl-methyl sulflde i 20.0 Sulfanilamldp 17,1 Aqueous formaldehyde (approx, 37.1%

HCHO)- .48.6 Sodium hydroxide in 2.5 parts water 0.05

A large mass ofiinsoluble resinous material was precipitated but enough. of the resin apparently dissolved to yield a syrupy mother liquor. When the resinous precipitate was heated on a 130 C.

hot plate a thermoplastic product was obtained.

A heat-curable resin was produced by incorpowere heated together under reflux for 15 minutes to yield a clear dark syrup. This syrup bodied to a solid resinous mass when heated on'a 130 C. hot plate. Satisfactory syrups also are obtained by using longer reflux periods.

Example 6 Parts 4,6-diamino s-triazinyl-z carbamyi-methyl sulfide 60.0 Butyl alcohol 111.0

Aqueous formaldehyde (approx. 37.1%

HCHO) 97.2 Aqueous ammonia (approx. 28% NI-Iz) .4... 6.0 Sodium hydroxide in 2.5 parts water 0.1

g The above components were heated together under reflux for 20 minutes. The resulting product, was a clear, light-colored resinous syrup. This syrup bodied readily toa thermoplastic resin when heated on a 130 C. hot plate. Heat-curable resins were produced by adding chloracetamide, sodium chloracetate, 'sulfamic acid and other active and latent curing catalysts'and curing reactants as described under Example 1. A small amount of hydrochloric acid also is suitable for converting the thermoplastic material to an inrating into the syrupy solution active or latent curing catalysts or by intercondensation' with curing reactants as described under, Example 1.

- The addition of sulfamic acid to the syrupy solution yielded a heat-convertible resin that cured Example 4 1 Parts 4,6-diamino s-triazinyl-Z carbamyl-methyl sulfldp 20.0 Dimethylol' urea (commercial grade containing approx. 11% by weight of water)- 40.5

Aqueous ammonia (approx. 28% NH3) 4.0 Sodiumhydroxidefin 2.5 parts water 0.05 Water a 60.0

The above components were heated together under reflux for 30 minutes, after which 0.5 part chloracetamidewas added and refluxing was continued for an additional 5 minutes. The resulting I syrupy condensation product was mixed with parts alpha cellulose and 0.2 part zinc stearate to form a molding compound. The wet compound was dried for 3.hours at 60 C. Samples of the dried compound were molded at 130 C. under a pressure of 2,000 pounds per square inch.

' In one case the time of molding was 4 minutes and in the other, 5 minutes. Both samples were well-cured throughout and showed good flow The molded pieces were light in color andhad a smooth finish.

. The sample which had been molded for 4 minutes was tested for water absorption as described under Example 1. The percentage of water re tained on this test was 4.08%. Example 5 1 Parts eam... .sl-triazinylz carbamyl-met 1 8111116? Acrolein g g 50.4 Sodium hydroxide in 0.5 part water 0.3).

rapidly under heat to an insoluble, infusible state.

soluble or cured state. The initial condensation product was soluble inboth water and ethyl alcohol.

Example 7 4 Parts 4,6-diamino s-triazinyl-2 carbamyl-methyl sulfide 60.0 Glycerin p 18.0 Aqueous formaldehyde (approx. 37.1%

HCHO) I 97.2 Aqueous ammonia (approx. 28% NH?) 5.0 Sodium hydroxide in 0.5 part'water 0.1

fusible state as compared with agents such, for

example, as hydrochloric acid. The product of this example would be especially suitable for use in modifying rapidly curing resins to control their curing characteristics.

Example 8 4,6-diamino s-triazinyl-Z carbamyl-methyl sulfide 60 0 Polyvinyl almhol' 792 Aqueous formaldehyde (approx. 37.1%

HCHO) 194.4 Sodium hydroxide in 1 part water 0.2 Water The above components were heated together under reflux for 15 minutes, resulting in a clear. light-colored resinous syrup; When a sample of this syrup was heated on a C. hot plate it bodied fairly rapidly to athermo-plastic mass. The addition of a small amount of dilute hydrochloric acid caused a rapidly thermosetting resin to be formed. A filmlof the unmodified resinous syrup of this example was baked on a glass Parts I Chloracetamid plate. The baked fllm was clear, transparent and hard. The product of this example is'especially suitable for use in the production of varnishes and as modifiers of other synthetic resinous materials.

Example 9 Parts 4,6-diamino s-triazinyl-2 carbamyl-methyl Sulfide 60.0 Diethyl ma'lnnat I 48.0

Aqueous formaldehyde (approx. 37.1%

HCHO) 145.8 Sodium hydroxide in 1 part water 0.2

were heated together under reflux for 15 minutes to yield a clear syrup. When this syrup was heated on a hot plate it slowly cured. Heatconvertible resins of rapid-curing characteristics are produced by adding active or latent curing catalysts or by intercondensation with curingreactants as described under Example 1. Sulfamic acid gave a 'thermosetting resin which cured more rapidly to the insoluble, iniusible state than was obtained by the use of chloracetamide.

. 4,6-diamino s-triazinyl-2 phenylcarbamyl- Exampledd Par s 4,6-diamino s-triazinyl-2 phenylcarbamylmethyl sulfide 27.6 Aqueous formaldehyde (approx. 37.1%

I-ICHO) 32.4 Sodium hydroxide in a small amount of water 0.03 Water V 15.0 Chloracetamide 0.3

All ofthe above components with the excep-' tion of the chloracetamide were heated together under reflux for 15 minutes. The chloracetamide was then added and refluxing was continued for an additional 5 minutes to cause the chloracetamide to intercondense with the partia1condensation product of the triazine derivative and formaldehyde. The resulting syrup was mixed with 21 parts alpha cellulose in flock form and 0.2 part of zinc stearate. The wet compound was dried at 60 C. until sufflciently free from moisture so that it could be molded satisfactorily.

-A sample of the dried compound was molded for 10 minutes at 135 C. \inder a pressure of 2,500 pounds per square inch. The molded piece was well-cured throughout.

All of the above components with the exception of the chloracetamide were heated together under reflux for 24 minutes. The chloracetamide was now added'a'ndrefluxing was continued for an additional 13 minutes. The pH of the resulting syrup was 4.55. This syrup was mixed with 21.9 parts alpha -cellulose and 0.2 part zinc stearate to form a molding compound. The wet compound was dried at 60 C. A heat-resistant piece having excellent cure and cohesive properties was obtained when a sample of the dried 4,6-diamino s-triazinyl-2 .Sodium hydroxide in a small amount of" Example 12 Parts methyl sulfide 20.7 Para-toluenesulfonamide. 12.8 Aqueous formaldehyde (approx. 37.1%

HCHO) 48.6

water 0.04

, were heated together under reflux for 15 minutes. The resinified syrup was treated with a curing agent, specifically chloracetamide in one case and sulfamic acid in another, and the mixture then refluxed until the curing agent had dissolved. The resulting product in each case was mixed with 27.5 parts alpha cellulose and 0.2

part zinc stearate to form molding compounds. The wet compounds were dried at C. and samples of the dried compounds then molded at 135 C. under a pressure of 2,000 pounds per square inch. Well-plasticized and well-cured molded pieces were obtained.

Example 13 1 Parts 4,6-diamino s-triazin'yl-2 phenylcarbamylmethyl sulfide Dimethylol urea (commercial grade containing approx. 11% by weight of water)- 53.5

Sodium hydroxide in 'a small amount of water Chloracetamide 0.4

Allof the above components with the excep tion of the chloracetamide were heated together under reflux for 25 minutes. The chloracetamide was now added and refluxing was continued for an additional 2 minutes. The pH of the resulting syrup was 5.34. A molding compound was made from this syrup by mixing it with 28.1

parts alpha cellulose and 0.2 part. zinc stearate.

The wet compound was dried at 60' C. A wellmolded piece was obtained by pressing a, sample of the dried compound for 5 minutes at 135 C. under a pressure of 2,000 pounds per square inch.

Example 14 Parts phenylcarbamylmethyl sulfide 1.9

Phenol-formaldehyde resinous partial con;

Example 11 9 Parts 4.6-diamino s-triazinyl-2 phenylcarbamylmethyl sulfide 8J0 Urea I 7.2

Aqueous formaldehyde (approx. 37.1% .HCHO) 48.6 Sodium hydroxide in a small amount of water compound was molded under heat and pressure.

densation product 60.0 Aqueous ammonia (approx. 28% NH3) 0.5 Oxalic a 1.1

The phenolic resin mentioned in the above formulawas prepared by heating a mixture of parts synthetic phenol, parts aqueous formaldehyde containing approximately 37.1% HCHO and 2.85 parts potassium carbonate at 65 C. for 4- cellent cohesive properties was obtained. The molding compound showed good flow characteristics during molding.

pounds'per square inch. A well-cured molded article having exutes.

Sodium hydroxide in a small amount oi."

.Jmmpl 1 p a Parts 4,6-diamino s-triazinyl-2 phenylcarbamylmethyl sulflde -'10.4 Acrol in 8.4 Sodium hydroxide in a small amount of water a s 0.01 Water 10.0

were heated together under reflux for 15 min- The resinified syrup is suitable for use in the production of molding compounds. Heatconvertible resinsv are produced by incorporating 1 either into the syrupy mass or into the dehydratedresin active or latent curing catalysts or by intercondensation with curing reactants as described under Example 1. Well-cured resins were produced by heating the reslnifled syrup with small amounts of citric acid, phthalic acid, sulfamic acid, etc., on a 140 C. hotplate.

EaiampZeIG Parts 4,6-diamino s-triazinyl-2 phenylcarbamylmethyl sulfide. 10.4 Eurfur l 15.8 Sodium .hydroxide inra small amount of water v were heated together under reflux for 15 minutes. The resulting product is suitable for use in the production ofmolding compounds. A heat-hard-- enable resinous composition is produced by incorporating into the resinous syrup or into the dehydrated resin active or latent curing catalysts or curing reactants such as described under-Example 1.

Example '17 4,6-diamino s-triazinyl-2 pheny-icarbamylmethyl sulfide 41.4 Aqueous formaldehyde (approx. 37.1%

HCHO) 48.6 Butyl 'alcohnl 55.5 Sodium hydroxide in a smallamount of waterwereheated together under reflux for 20 minutes. The resulting syrup was dehydrated by heating it on asteam plate. The dehydrated syrup was found to be soluble in solvents such, for example, as ethyl alcohol, Solvatone, ethylene glycol, etc. The solubility and film-forming characteristics Parts 1 Sodium hydroxide in example'would be suitable for use where slowl'r The plasticizing efiect of the acetamide was evident from the relatively slow curing of the dehydrated resin when tested on a. 140 hot plate.

Active or latent curing catalysts or curing reactants of the kinds mentioned underExample i may be added as desired. The product of this curing resins are advantageous.

Example 19 I Parts 4,6-diamino s-triazinyl-2 phenylcarbamylmethyl sulfide 20.7 Diethyl malonate '12.0 Aqueous formaldehyde (approx. 37.1%

HCHO), 48.6

a small amount of water 0.04

. were heated together under reflux for 25 minutes.

I resinifled syrup is soluble in solvents such, for

of this resin make it especially suitable for use I in the production of spirit and baking varnishes. It may be used as a modifier oi varnishes oi the aininoplast and alkyd-resin types. Heat-hard-. enable resins are produced by incorporating into the resinous syrup active or latent curing catalysts or by intercondensation with curing reactants as described under Example 1. A film of the resinous syrup catalyzed with a small amount of hydrochloric acid was applied to a glass plate, which thereafter was baked for several hours at C. A hard, transparent, baked fllm of glossy appearance was produced on the plate.

' Example 18 Parts 4,6-diamino s-triazinyl-2 phenylcarbamylmethyl sulfide 20.7 I

Acetamide Aqueous. formaldehyde HCHO) (approx. 7 37.1%

water 0.04

4 were heated together under reflux for 20 minutes The clear resinous syrup thereby produced was dehydrated by heating it on a steam plate. The

example, as ethyl alcohol, Solvatone, and ethylene glycol. This resin may be used in the production of varnishes as described under Example 17.

Example 21 I Parts 4,6-diamino s-triazinyl-2 phenylcarbamylmethyl sulfide 20.7 vPolyvinyl alcohol 3.4

Aqueous formaldehyde (approx. 37.1%

HCHO) 48.6

Sodium hydroxide in a small amount of water 0.04

Water 100.0

were heated together under reflux for 20 minutes. This resulted in the formation of a partly resinifled syrup. This syrup is suitable for use in the manufacture of baking varnishes. When this resinous syrup was treated with a curing agent,

specifically a small amount of hydrochloric acid,

and the resulting product baked in film form on' a glass surface for several hours at 60 C., a baked film that was opaque, hard, water-resistant, smooth and that adhered tightly to the glass surface was obtained. The resinous composition of this example also may be used in the preparation of moldingcompounds after incorporating therein active or latent curing catalysts or curing reactants as described under Example 1.

In producing these new condensation products the choice of the aldehyde is dependent largely upon economic considerations and upon the particular properties desired in the finished product. We prefer to use as the aldehydic reactant formaldehyde or compounds engendering formaldehyde, e. g paraformaldehyde, hexamethylene tetramine, etc. Illustrative examplesof other aldehydes that may be used are acetaldehyde, propionaldehyde, butyraldehyde, methacholein, crotonaldehyde, benzaldehyde, furfural, etc., mixtures thereof, or mixtures of formaldehyde (or compounds engendering formaldehyde) with suchaldehydes. Illustrative examples of aldehyde-addition products that may be used instead of the aldehydes themselves are the monoand poly-(N-carbinol) derivatives, more particularly the monoand poly-methylol derivatives, of urea, thiourea, selenourea and iminourea, and oi. substituted ureas, thioureas, selenour'eas and iminoureas (numerous examples of which are given in DAlelio copending application Serial No. 377,524, monoand poly-(N-carbinol) derivatives of amides of polycarboxylic acids, e. g., maleic, itaconic, fumaric, adipic, malonic, succinic, citric, phthalic, etc., monoand poly-(N-carbinol). derivatives of amidogentriazines, numerous examples of which are given in DAlelio copending application Serial No. 377,524. Particularly good results are obtained with active methylene-containing bodies such as monoand di-methylol ureas and the methylol melamines, e. g., mono-.

. di-, tri-, tetra-, pentaand hexa-methylol melamines. Mixtures of aldehydes and active methylene-containing bodies may be employed, e. g.,

mixtures of formaldehyde and methylol compounds such, for instance, as dimethylol urea and trimethylol melamine.

The ratio of the aldehydric reactant to the triazine derivative may be varied over a wide range, but ordinarily the reactants are employed in an amount corresponding to at least one mol of the aldehyde, specifically formaldehyde, for each mol of the triazine derivative. Thus we may use, for example, from one to five or six mols of an aldehyde for each mol of triazine derivative. When the aldehyde is available for reaction in the form of an alkylol derivative, more particularly a methylol derivative such, for instance, as dimethylol urea, trimethylol melamine, etc., then higher amounts of such aldehyde-addition products ordinarily are used, for example, up to or 12 mols of such alkylol derivatives for each mol of the-triazine derivative. s

As indicated hereinbefore, and as further shown by a number of the examples, the properties of the fundamentalresins of this invention may be varied widely by introducing other modifying bodies before, during or after effecting condensation between the primary components.

Thus, as modifying agents we may use, for instance, monohydric alcohols such as ethyl, propyl, isopropyl, isobutyl, hexyl, etc., alcohols; polyhydric alcohols such as diethylene glycol, triethylene glycol, pentaerythritol, etc.; amides such as formamide, stearamide, acrylamide, benzamide, toluene sulfonamides, benzene 'disulfonamides, benzene trisulfonamides, adipic diamide, phthalamide, etc.; amines such as ethylene diamine, phenylene diamine, etc. phenol and substituted phenols, including aminophenols, etc.; ketones, including halogenated ketones; nitriles, e. g., acrylonitrile, methacrylonitrile, succinonitrile, including halogenatednitriles, etc.; and others.

The modifying bodies also may takev the form of high molecular weight bodies with or without resinous characteristics, for example, hydrolyzed wood products, formalized cellulose derivatives, lignin, protein-aldehyde condensation products, resinous reaction products of aldehydes, for example formaldehyde, with the aminotriazoles (e. g., guanazole, phenyl guanazole, etc.), alone or admixed with, for example, urea, melamine, or

urea and melamine, resins obtained b'yreaction amine. Other examples of modifying bodies are the urea-aldehyde condensation products, the

aniline-aldehyde condensation products, furfural condensation products, phenol-aldehyde condensation products, modified or unmodified, saturated or unsaturated polyhydric alcohol-polycarboxylic acid condensation products, water-soluble cellulose derivatives. natural gums and resins such as shellac, rosin, etc.; polyvinyl compounds such as polyvinyl esters, e.g., polyvinyl acetate, polyvinyl butyrate, etc., polyvinyl ethers including polyvinyl acetals, specifically polyvinyl formal, etc.

Instead of effecting reaction between a. triazinyl carbamyl-alkyl sulfide (or a triazinyl thiocarb-amyl-alkyl sulfide) of the kind herein described and an aldehyde, e. g., formaldehyde, we may cause an aldehyde to condense with a salt of the triazine derivative or with a mixture of the triazine derivative and a salt (organic or inorganic) thereof. As examples of salts of the triazine derivatives that may be used, we mention salts of monoand di-amino s-triazinyl carbamyl-methyL' carbamyl-ethyl, thiocarbamylmethyl and thiocarbamyl-ethyl sulfides and organic or inorganic acids as, for instance, hydrochloric, sulfuric, phosphoric, boric, acetic, chloracetic, propionic, butyric, valeric, acrylic, polyacrylic, methacrylic, polymethacrylic, oxalic. m-alonic, succinic, adipic, malic, malei'c, fumaric. benzoic, salicylic, camphoric, phthalic, etc.

Dyes, pigments, plasticizers, mold lubricants, opacifiers and various fillers (e. g., wood flour, glass fibers, asbestos, including defibrated asbestos, mineral wool, mica, cloth cuttings, etc.) may be compounded with the resin in accordance, with conventional practice to provide various thermoplastic and thermosetting molding composisynthetic resins, as laminating'varnishes in the production of laminated articles wherein sheet materials, e. g., paper, cloth, sheet asbestos, etc., are coated and impregnated with the resin, superimposed and thereafter united under heat and pressure. They may be used in the production of wire or bakingenamels, for bonding or cementing together mica flakes to form a laminated mica article, for bonding together abrasive.

grains in the production of resin-bonded abrasive articles such, for instance, as grindstones, sandpapers, etc., in the manufacture of electrical resistors, etc. They also may be employed for treating cotton, linen and other cellulosic materials in sheet or other form. They also may be used as impregnants for electrical coils and for other electrically insulating applications.

What we claim as new and desire to secure by Letters Patent of the United States is:

1. A composition of matter comprising the re- 8 action product of ingredients comprising aldehyde and an organic sulfide corresponding to thegeneralformula c muc I where n is an integer and is ?at least 1 and not more than 3, a: ban integer and is at least 1 and not more than 2, R is a member of the class consisting of hydrogen and monovalent hydrocarbon and halo-hydrocarbonradicals, and Y is a member of the class consisting of oxygen and sulfur.

2. A composition as in claim lwherein the aldehyde is formaldehyde.

3. A compositioncomprising a condensation product of ingredients comprising an aldehyde and an organic sulfide corresponding to the general formula Y ll I where n is an integer and isat least 1 and not more than 3, :r is an integer and is at least 1 and not more than 2, Y is a member of the class con? sisting of oxygen andsulfur, and R represents hydrogen. 3

4. A composition comprising a condensation product of ingredients comprising an aldehyde and an-organic sulfidecorresponding to the general'formula where n is an integer and is at least 1 and not more than 3, a: is an integer and'is at least 1 and not more than 2, R representshydrogen and Y 1 represents oxygen.

5. A composition comprising a condensation product of ingredients comprising formaldehyde and an organic sulfide corresponding to the general formula 11 I Q, 5(CR:)CNHR N L i Y i where n is an integer and is at least 1 and not more than 3, a: is 1, R represents hydrogen and Y represents oxygen.

6. A resinous composition comprising the product of reaction of ingredients comprising symj where nis an integrland is at least 1 and not aldehyde and 4,6-diamino s-triazinyl-2 carbamylmethyl sulfide.

10. A heat-curable resinous condensation product of ingredients comprising formaldehyde and an organic sulfide corresponding to the general formula Y 1 represents hydrogen and 14."A composition comprising the product of reaction of ingredients comprising urea, a diamino s-triazinyl carbamyl-methyl sulfide and an aldehyde.

15. A composition comprising the product of reaction of ingredientscomprising melamine, a diamino s-tria zinyl carbamyl-methyl sulfide and formaldehyde. 1

16. A composition comprising the product of reaction'of ingredients comprising a phenol, an aldehyde and an organic sulfide corresponding to the general formula where n is an integer and is at least 1 and not more than 3, a: is an integer and is at least 1 and not more than 2, His a member of the class consistingof hydrogen and monovalent hydrocarbon and halo-hydrocarbon radicals, and Y is a member of the class consisting of oxygen and sulfur.

17. A heat-curable composition comprising the heat-convertible product of reaction of (1) a partial condensation product of ingredients comprising urea, a diamino s-triazinyl carbamylmethyl sulfide and formaldehyde and (2) a chlorinated acetamide.

18. [A product comprising the heat-cured composition of claim 17.

'19. The method of preparing, new condensation products which comprises eifecting reaction between ingredients comprising an aldehyde and an organic sulfide corresponding to the general metrical triazinyl-2,4,6 tri-(carbamyl-methyl sultide) and an aldehyde.

7. A resinous composition comprising the-product of reaction of ingredients comprising a monoamino 's-triazinyl di-(earbamyl-methyl sulfide) 7 and an aldehyde.

8. A resinous composition comprising the product of reaction of ingredients comprising a diamino s-triazinyl carb'amyl-methyl sulfide and an aldehyde.

9. A resinous composition comprising the product of reaction ofingredients comprising formformula where n is an integer and is at least 1 and'not more than 3, a: isan integer and is at least 1 and not more than 2, R is a member of the class consisting of hydrogen and monovalent hydrocarbon and halo-hydrocarbon radicalsandY is a member oi theclass consisting of oxygen and sulfur.

GAETANO F. DALELIO. JAMES W. UNDERWOOD.

CERTIFICATE OF CORRECTION.

Patent No. 2,517,758. April 27, 1915.

GAETANO F. D'ALELIO, ET AL.

It is hereby certified that error appears in the printed specification of the above numb ered patent requiring correction as follows: Page 1, first column, line 10, for "malamine" read -melamine-; page 7, first column, line l, for methacholein read -methacr0lein-- and that 'the said Letters Patent should be read with this correction therein that the same may conform to the record of the case in the Patent Office.

Signed and sealed this 15th day of June, A. D. 1915.

Henry Van Arsdale, (Seal) Acting Commissioner of Patents. 

